This invention relates to metal complexes and to addition polymerization catalysts formed therefrom that have improved catalytic performance. More particularly the present invention relates to an addition polymerization catalyst composition comprising a Group 3, 4, or Lanthanide metal complex containing a boratabenzene group or divalent derivative thereof bonded via its delocalized xcfx80 electrons to the metal (also referred to as a boracyclohexadienyl group). In addition, the present invention relates to certain of the foregoing complexes possessing a novel bridged structure. Finally, the invention relates to a method of using the foregoing catalyst compositions in an addition polymerization process for polymerizing addition polymerizable monomers.
In EP-A-416,815 there are disclosed certain constrained geometry metal complexes and catalysts derived by reacting the metal complex with activating cocatalysts. Supported derivatives of such catalysts were prepared by contacting them with a support such as alumina, silica or MgCl2. In U.S. Pat. No. 5,064,802 (EP-A-418,044) there are disclosed certain further catalysts formed by reacting metal complexes with ion forming activating cocatalysts that are salts of Bronsted acids containing a non-coordinating compatible anion. The reference discloses the fact that such complexes are usefully employed as catalysts in addition polymerizations. In EP-A-520,732 an alternative technique for preparing cationic constrained geometry catalysts using borane activators is disclosed.
In U.S. Pat. No. 4,892,851 there are disclosed biscyclopentadienyl Group 4 metal complexes, especially complexes of zirconium or hafnium that are usefully employed with alumoxane activating cocatalysts for use in addition polymerizations, especially the polymerization of aliphatic xcex1-olefins. In a series of patents, W. Spaelick has disclosed certain ring substituted stereorigid bisindenyl complexes and their use as olefin polymerization catalysts. The bridging group of such complexes generically includes silicon, germanium or tin containing divalent groups containing hydride, halogen, C1-10 alkyl, C6-10 fluoroalkyl, C6-10 aryl, C6-10 fluoroaryl, C1-10 alkoxy, C2-10 alkenyl, C7-40 aralkyl, C8-40 aralkenyl or C7-40 alkylaryl groups or ring forming combinations thereof. Such disclosure may be found in U.S. Pat. No. 5,243,001, U.S. Pat. No. 5,145,819, U.S. Pat. No. 5,304,614, U.S. Pat. No. 5,350,817, among others.
Boratabenzenes are anionic ligands which are boron containing six membered ring systems. They are previously known in the art having been described by A. Ashe, et al., J. Am. Chem. Soc., 93, 1804-1805 (1971). They may be prepared by reaction of 1,1-diorgano-1-stannacyclohexa-2,5-diene and a borontrihalide followed by substitution with a hydrocarbyl, amino, silyl or germyl group. Such ligand groups correspond to the formula: 
wherein J is selected from the group consisting of hydrogen, hydrocarbyl, dihydrocarbylamino, silyl, germyl, halohydrocarbyl, or halocarbyl, said J having up to 20 non-hydrogen atoms.
It would be desirable if there were provided an improved catalyst system based on the foregoing boratabenzene groups as well as an improved addition polymerization process utilizing such catalyst systems.
As a result of investigations carried out by the present inventors there have now been discovered new and improved Group 3, 4, or Lanthanide metal complexes corresponding to the formula: 
or a dimer, solvated adduct, chelated derivative or mixture thereof,
wherein:
Y is a divalent derivative of a boratabenzene group or a hydrocarbyl-, dihydrocarbylamino-, silyl- or germyl-substituted boratabenzene group containing up to 50 nonhydrogen atoms that is bonded via its delocalized xcfx80-electrons to M;
L is Y or a hydrocarbadiyl group that is bound to M by means of its delocalized xcfx80-electrons, or L is a monovalent or divalent amido group, said L group containing up to 50 nonhydrogen atoms;
M is a metal of Group 3, 4 or the Lanthanide series of the Periodic Table of the Elements;
Z is a covalently bound, divalent substituent of up to 50 non-hydrogen atoms having the formula, xe2x80x94(ER22)mxe2x80x94, wherein E independently each occurrence is carbon, silicon or germanium, R2 independently each occurrence is selected from the group consisting of hydrocarbyl, hydrocarbyloxy, silyl, and germyl of up to 20 atoms other than hydrogen, and m is an integer from 1 to 3;
Xxe2x80x2 is a neutral ligand having up to 20 non-hydrogen atoms;
Xxe2x80x3 independently each occurrence is a monovalent, anionic moiety selected from hydride, halo, hydrocarbyl, silyl, germyl, hydrocarbyloxy, dihydrocarbylamide, siloxy, halohydrocarbyl, halosilyl, silylhydrocarbyl, and dihydrocarbylaminohydrocarbyl having up to 20 non-hydrogen atoms, or two Xxe2x80x3 groups together form a divalent hydrocarbadiyl group;
n is a number from 0 to 3; and
p is an integer from 0 to 2.
According to the present invention there are further provided improved addition polymerization catalyst compositions comprising an activating cocatalyst and one or more Group 3, 4 or Lanthanide metal complexes corresponding to the formula: 
or a dimer, solvated adduct, chelated derivative or mixture thereof,
wherein:
Yxe2x80x2 is a boratabenzene group or a hydrocarbyl-, dihydrocarbylamino-, silyl- or germyl-substituted boratabenzene group containing up to 50 nonhydrogen atoms that is bonded via its delocalized xcfx80-electrons to M;
Lxe2x80x2 is Yxe2x80x2 or a hydrocarbyl group that is bound to M by means of its delocalized xcfx80-electrons, or Lxe2x80x2 is an amido group, said Lxe2x80x2 group containing up to 50 nonhydrogen atoms;
L and Y are as previously defined;
M is a metal of Group 3, 4 or the Lanthanide series of the Periodic Table of the Elements;
Z is a covalently bound, divalent substituent of up to 50 non-hydrogen atoms having the formula, xe2x80x94(ER22)mxe2x80x94, wherein E independently each occurrence is carbon, silicon or germanium, R2 independently each occurrence is selected from the group consisting of hydrocarbyl, hydrocarbyloxy, silyl, and germyl of up to 20 atoms other than hydrogen, and m is an integer from 1 to 3;
Xxe2x80x2 is a neutral ligand having up to 20 non-hydrogen atoms;
Xxe2x80x3 independently each occurrence is a monovalent, anionic moiety selected from hydride, halo, hydrocarbyl, silyl, germyl, hydrocarbyloxy, dihydrocarbylamide, siloxy, halohydrocarbyl, halosilyl, silylhydrocarbyl, and dihydrocarbylaminohydrocarbyl having up to 20 non-hydrogen atoms, or two Xxe2x80x3 groups together form a divalent hydrocarbadiyl group;
n is a number from 0 to 3; and
p is an integer from 0 to 2,
provided that when two Y groups or two Yxe2x80x2 groups are present in the complex, then the activating cocatalyst does not consist solely of an alumoxane.
In a further embodiment there is provided a supported catalyst system comprising one or more of the foregoing metal complexes, one or more activating cocatalysts, and a support material.
Finally there is provided an improved method for polymerization of addition polymerizable monomers using one or more of the above catalyst compositions or catalyst systems. Such addition polymerization processes may be used to prepare polymers for use in making molded articles, films, sheets, foamed materials and in other industrial applications.
All reference to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 1989. Also, any reference to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups. As used herein, the term xe2x80x9caminoxe2x80x9d refers to a hydrocarbyl or dihydrocarbyl substituted nitrogen group attached to a nonmetal or to a metalloid. The term xe2x80x9camidoxe2x80x9d refers to such a hydrocarbyl or dihydrocarbyl group attached to a metal.
Suitable Lxe2x80x2 groups for use herein include any cyclic, neutral or anionic Relectron containing moiety capable of forming a delocalized bond with the Group 3, 4 or Lanthanide metal. Examples of such neutral groups include arene moieties such as benzene, anthracene or naphthalene, as well as hydrocarbyl-, silyl- or germyl-substituted derivatives of such groups. Examples of anionic xcfx80-electron containing moieties include cyclopentadienyl groups, cyclohexadienyl groups, 1,3-pentadienyl groups, and allyl groups, as well as hydrocarbyl-, silyl- or germyl-substituted derivatives of such groups, and partially hydrogenated derivatives of the cyclic groups. In addition, suitable Lxe2x80x2 groups include the aforementioned boratabenzene or substituted boratabenzene groups represented by Yxe2x80x2. In complexes involving divalent derivatives of such groups, e. g. L or Y groups, it is understood that another atom of the complex is also bonded to such cyclic group thereby forming a bridged system.
By the term xe2x80x9cderivativexe2x80x9d when used to describe the above cyclic substituted, delocalized xcfx80-bonded groups is meant that each atom in the delocalized xcfx80-bonded group may independently be substituted with a radical selected from the group consisting of hydrocarbyl radicals, halo-, cyano or dialkylamino- substituted-hydrocarbyl radicals, and hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from Group 14 of the Periodic Table of the Elements. Suitable hydrocarbyl and substituted-hydrocarbyl radicals used to form derivatives of the substituted, delocalized xcfx80-bonded group will contain from 1 to 20 carbon atoms and include straight and branched alkyl radicals, cycloalkyl radicals, aryl radicals, alkyl-substituted cycloalkyl radicals, and alkyl-substituted aromatic radicals. In addition two or more such radicals may together form a fused ring system which may be saturated or unsaturated. Examples of the latter are indenyl-, tetrahydroindenyl-, fluorenyl-, and octahydrofluorenyl- groups, as well as multicyclic, fused ring, boratabenzene derivatives. Suitable hydrocarbyl-substituted organometalloid radicals include mono-, di- and trisubstituted organometalloid radicals of Group 14 elements wherein each of the hydrocarbyl groups contains from 1 to 20 carbon atoms. More particularly, suitable hydrocarbyl-substituted organometalloid radicals include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, trimethylgermyl and the like.
Preferred L groups are Y, divalent hydrocarbyl substituted amido groups such as a t-butylamido group, and cyclic, hydrocarbadiyl groups. Examples of the latter include divalent derivatives of cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, cyclohexadienyl, dihydroanthracenyl, hexahydro-anthracenyl, and decahydroanthracenyl groups, and C1-10 hydrocarbyl-substituted derivatives thereof. Most preferred L groups are divalent derivatives of tetramethylcyclopentadienyl, 2-methylindenyl, 3-methylindenyl, 2,3-dimethylindenyl, 2,3,5,6-tetramethylindenyl, and 2,3,5,6,7-pentamethylindenyl.
Preferred Z groups are 1,2-ethanediyl, dimethylsilanediyl, diphenylsilanediyl, methylisopropoxysilanediyl, and methylphenylsilanediyl.
P referred Yxe2x80x2 groups correspond to the formula: 
wherein R1 independently each occurrence is hydrogen, hydrocarbyl, dihydrocarbylamino, disilylamino, hydrocarbylsilylamino, halohydrocarbyl, halocarbyl, silyl, germyl, or mixtures thereof, said R1 having up to 50, preferably up to 20 non-hydrogen atoms, and optionally two such R1 groups may be joined together thereby forming a fused ring derivative, and further optionally two such Yxe2x80x2 groups may be joined together in a multiple ring system. In complexes involving divalent derivatives of such Yxe2x80x2 groups, one R1 is a covalent bond or a divalent derivative of one of the foregoing substituent groups, said R1 being also bonded to another atom of the complex thereby forming a bridged system.
More preferred Yxe2x80x2 groups are 1-phenyl-, 1-(N,N-di-(C1-8alkyl), 1-benzyl-, and 1-methyl- substituted boratabenzene groups. Preferred Y groups are divalent derivatives of the foregoing Yxe2x80x2 groups. Highly preferably, the divalent derivative of the boratabenzene ligand is substituted with a C1-10 hydrocarbyl group in the ring position that is meta to the bridgehead. The skilled artisan will appreciate that the various L and Y ligand groups may be connected at any position of the boratabenzene ring, thereby forming various isomeric products. Mixtures of such isomers may also be utilized.
Examples of highly preferred complexes according to the present invention correspond to the formula: 
wherein:
M is titanium, zirconium or hafnium, preferably zirconium, in the +2, +3, or +4 formal oxidation state;
Z is a covalently bound, divalent substituent of up to 50 non-hydrogen atoms having the formula, xe2x80x94(ER22)mxe2x80x94, wherein E independently each occurrence is carbon, silicon or germanium, R2 independently each occurrence is selected from the group consisting of hydrocarbyl, hydrocarbyloxy, silyl, and germyl of up to 20 atoms other than hydrogen, and m is an integer from 1 to 3;
Y in each occurrence, independently is a divalent derivative of a boratabenzene group or a hydrocarbyl-, dihydrocarbylamino-, silyl- or germyl-substituted boratabenzene group containing up to 50 nonhydrogen atoms that is bonded via its delocalized xcfx80-electrons to M;
Xxe2x80x2 is a conjugated diene having from 4 to 30 non-hydrogen atoms, which forms a xcfx80-complex with M when M is in the +2 formal oxidation state, whereupon n is 1 and p is 0; and
Xxe2x80x3 each occurrence is an anionic ligand group that is covalently bonded to M when M is in the +3 or +4 formal oxidation state, whereupon n is 0 and p is 1 or 2, and optionally two Xxe2x80x3 groups together form a divalent anionic ligand group.
Examples of suitable Xxe2x80x2 moieties include: xcex74-1,4-diphenyl-1,3-butadiene; xcex74-1,3-pentadiene; xcex74-1-phenyl-1,3-pentadiene; xcex74-1,4-dibenzyl-1,3-butadiene; xcex74-2,4-hexadiene; xcex74-3-methyl-1,3-pentadiene; xcex74-1,4-ditolyl-1,3-butadiene; and xcex74-1,4-bis(trimethylsilyl)-1,3-butadiene. Of the foregoing 1,4-diphenyl-1,3-butadiene, 1-phenyl-1,3-pentadiene, and 2,4 hexadiene are preferred.
Examples of suitable Xxe2x80x3 moieties include chloride, methyl, benzyl, phenyl, tolyl, t-butyl, methoxide, and trimethylsilyl or two Xxe2x80x3 groups together are 1,4-butanediyl, s-cis(1,3-butadiene), or s-cis(2,3-dimethyl-1,3-butadiene).
Preferred Z groups are those wherein E is carbon and m is 2 or where E is silicon and m is 1. Also preferably R2 is methyl, phenyl, methoxide, ethoxide, propoxide or butoxide.
In the most preferred embodiment xe2x80x94Yxe2x80x94Zxe2x80x94Yxe2x80x94 conforms to one of the following formulas: 
Wherein:
R1 independently each occurrence is hydrogen, hydrocarbyl, dihydrocarbylamino, perfluorohydrocarbyl, silyl substituted hydrocarbyl, or hydrocarbyl substituted silyl of up to 20 nonhydrogen atoms, and optionally two adjacent R1 groups together form a divalent derivative, thereby forming a multicyclic, fused, divalent derivative of a boratabenzene ring system; and
R2 is as previously defined.
Most preferably R1 independently each occurrence is hydrogen, C6-20 aryl, secondary or tertiary C3-10 alkyl, or di-C1-6 alkylamino, and R2 independently each occurrence is C1-4 alkyl or alkoxy.
In the foregoing structures a negative charge is delocalized on each boratabenzene ring. Both meso and racemic isomers of the metal complexes are obtainable.
Illustrative derivatives of Group 3, 4 or Lanthanide metals of the foregoing formula that may be employed in the practice of the present invention include:
[bis(xcex76-1-phenylboratabenzene-4-yl)dimethylsilane]zirconium (II) 1,4-diphenyl-1,3-butadiene,
[bis(xcex76-1-methyl-2-phenylboratabenzene-4-yl)dimethylsilane]zirconium (II) 1,4-diphenyl-1,3-butadiene,
[bis(xcex76-1-phenyl-2-methylboratabenzene-4-yl)dimethylsilane]zirconium (II) 1,4-diphenyl-1,3-butadiene,
[bis(xcex76-1-phenylboratabenzene-4-yl)dimethylsilane]titanium (II) 1,3-pentadiene,
[bis(xcex76-1-methylboratabenzene-4-yl)dimethylsilane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[bis(xcex76-1-phenylboratabenzene-4-yl)dimethylsilane]zirconium (IV) dimethyl,
[bis(xcex76-1-methyl-2-phenylboratabenzene-4-yl)dimethylsilane]zirconium (IV) dimethyl,
[bis(xcex76-1-phenylboratabenzene-4-yl)dimethylsilane]zirconium (IV) dibenzyl,
[bis(xcex76-1-phenylboratabenzene-4-yl)dimethylsilane]zirconium (IV) dichloride,
[bis(xcex76-1-methylboratabenzene-4-yl)dimethylsilane]zirconium (IV) dimethyl,
[1,2-bis(xcex76-1-methyl-2-phenylboratabenzene-4-yl)ethane]zirconium (IV) dibenzyl,
[bis(xcex76-1-phenylboratabenzene-4-yl)dimethylsilane]zirconium (IV) dichloride,
[1-(xcex76-1-phenylboratabenzene-2-yl)-2-(xcex76-1-phenylboratabenzene-3-yl)-ethane]zirconium (II) 1,4-diphenyl-1,3-butadiene,
[bis(xcex76-1-methylboratabenzene-3-yl)dimethylsilane]zirconium (II) 1,3-pentadiene,
[(xcex76-1-phenylboratabenzene-3-yl (xcex76-1-phenylboratabenzene-4-yl)dimethylsilane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[(xcex76-1-phenylboratabenzene-3-yl) (xcex76-1-phenylboratabenzene-4-yl)dimethylsilane]zirconium (IV) dimethyl,
[(xcex76-1-phenylboratabenzene-2-yl) (xcex76-1-phenylboratabenzene-4-yl)dimethylsilane]zirconium (IV) dibenzyl,
[(xcex76-1-phenylboratabenzene-2-yl) (xcex76-1-phenylboratabenzene-4-yl)dimethylsilane]zirconium (IV) dichloride,
[bis(xcex76-1-phenylboratabenzene-3-yl)dimethylsilane]zirconium (IV) dimethyl,
[(xcex76-1-phenylboratabenzene-2-yl) (xcex76-1-phenylboratabenzene-3-yl)dimethylsilane]zirconium (IV) dibenzyl,
[(xcex76-1-methylboratabenzene-2-yl)(xcex76-1-phenylboratabenzene-4-yl)dimethylsilane]zirconium (IV) dichloride,
[bis(xcex76-1-(N,N-dimethylamino)boratabenzene-4-yl)dimethylsilane]zirconium (II) 1,4-diphenyl-1,3-butadiene,
[bis (xcex76-1-(N,N-dimethylamino)boratabenzene-4-yl)dimethylsilane]titanium (II) 1,3-pentadiene,
[bis(xcex76-1-(N,N-dimethylamino)boratabenzene-4-yl)dimethylsilane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[bis(xcex76-1-(N,N-dimethylamino)boratabenzene-4-yl)dimethylsilane]zirconium (IV) dimethyl,
[bis(xcex76-1-(N,N-dimethylamino)boratabenzene-4-yl)dimethylsilane]zirconium (IV) dibenzyl,
[bis(xcex76-1-(N,N-dimethylamino)boratabenzene-4-yl)dimethylsilane]zirconium (IV) dichloride,
[bis(xcex76-1-(N,N-dimethylamino)boratabenzene-4-yl)dimethylsilane]zirconium (IV) dimethyl,
[bis(xcex76-1-(N,N-dimethylamino)boratabenzene-4-yl)dimethylsilane]zirconium (IV) dibenzyl,
[bis(xcex76-1-(N,N-dimethylamino)boratabenzene-4-yl)dimethylsilanezirconium (IV) dichloride,
[1-(xcex76-1-(N,N-dimethylamino)boratabenzene-2-yl)-2-(xcex76-1-dimethylamino)-boratabenzene-3-yl)ethane]zirconium (II) 1,4-diphenyl-1,3-butadiene,
[bis(xcex76-1-(N,N-dimethylamino)boratabenzene-3-yl)dimethylsilane]zirconium (II) 1,3-pentadiene,
[(xcex76-1-(N,N-dimethylamino)boratabenzene-3-yl)(xcex76-1-(N,N-dimethylamio)-boratabenzene-4-yl)dimethylsilane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[(xcex76-1-(N,N-dimethylamino)boratabenzene-3-yl) (xcex76-1-(N,N-dimethylamino)-boratabenzene-4-yl)dimethylsilane]zirconium (IV) dimethyl,
[(xcex76-1-(N,N-dimethylamino)boratabenzene-2-yl) (xcex76-1-(N,N-dimethylamino)-boratabenzene-4-yl)dimethylsilane]zirconium (IV) dibenzyl,
[(xcex76-1-(N,N-dimethylamino)boratabenzene-2-yl) (xcex76-1-(N,N-dimethylamino)-boratabenzene-4-yl)dimethylsilane]zirconium (IV) dichloride,
[bis(xcex76-1-(N,N-dimethylamino)boratabenzene-3-yl)dimethylsilane]zirconium (IV) dimethyl,
[(xcex76-1-(N,N-dimethylamino)boratabenzene-2-yl) (xcex76-1-(N,N-dimethylamino)-boratabenzene-4-yl)dimethylsilane]zirconium (IV) dibenzyl,
[1-(xcex76-1-(N,N-dimethylamino)boratabenzene-2-yl)-2-(xcex76-1-(N,N-dimethylamino)-boratabenzene-4-yl)ethane]hafnium (IV) dichloride,
[(xcex76-1-(N,N-diisopropylamino)boratabenzene-3-yl) (xcex76-1-(N,N-dimethylamino)-boratabenzene-4-yl)dimethylsilane]zirconium (IV) dimethyl,
[(xcex76-1-(N,N-diisopropylamino)boratabenzene-2-yl) (xcex76-1-(N,N-dimethylamino)-boratabenzene-4-yl)dimethylsilane]zirconium (IV) dibenzyl,
[(xcex76-1-(N,N-diisopropylamino)boratabenzene-2-yl) (xcex76-1-(N,N-dimethylamino)-boratabenzene-4-yl)dimethylsilane]zirconium (IV) dichloride,
[bis(xcex76-1-(N,N-diisopropylamino)boratabenzene-3-yl)dimethylsilane]zirconium (IV) dimethyl,
[(xcex76-1-(N,N-diisopropylamino)boratabenzene-2-yl) (xcex76-1-(N,N-dimethylamino)-boratabenzene-4-yl)dimethylsilane]zirconium (IV) dibenzyl,
[1-(xcex76-1-(N,N-diisopropylamino)boratabenzene-2-yl)-2-(xcex76-1-(N,N-dimethylamino)-boratabenzene-4-yl)ethane]hafnium (IV) dichloride,
[1,2-bis(xcex76-1-(N,N-dimethylamino)boratabenzene-4-yl)ethane]zirconium (IV) dimethyl,
[1,2-bis(xcex76-1-(N,N-dimethylamino)boratabenzene-4-yl)ethane]zirconium (IV) dibenzyl,
[1,2-bis(xcex76-1-(N,N-dimethylamino)boratabenzene-4-yl)ethane]zirconium (IV) dichloride,
[1,2-bis(xcex76-1-(N,N-diisopropylamino)boratabenzene-4-yl)ethane]zirconium (IV) dimethyl,
[1,2-bis(xcex76-1-(N,N-diisopropylamino)boratabenzene-4-yl)ethane]zirconium (IV) dibenzyl,
[1,2-bis(xcex76-1-(N,N-diisopropylamino)boratabenzene-4-yl)ethane]zirconium (IV) dichloride,
[2,2-bis(xcex76-1-(N,N-dimethylamino)boratabenzene-4-yl)propane]zirconium (IV) dimethyl,
[2,2-bis(xcex76-1-(N,N-dimethylamino)boratabenzene-4-yl)propane]zirconium (IV) dibenzyl,
[2,2-bis(xcex76-1-(N,N-dimethylamino)boratabenzene-4-yl)propane]zirconium (IV) dichloride,
[2,2-bis(xcex76-1-(N,N-diisopropylamino)boratabenzene-4-yl)propane]zirconium (IV) dimethyl,
[2,2-bis(xcex76-1-(N,N-diisopropylamino)boratabenzene-4-yl)propane]zirconium (IV) dibenzyl,
[2,2-bis(xcex76-1-(N,N-diisopropylamino)boratabenzene-4-yl)propane]zirconium (IV) dichloride,
[1-(xcex76-boratabenzene-2-yl)-2-(xcex76-boratabenzene-3-yl)ethane]zirconium (II) 1,4-diphenyl-1,3-butadiene,
[bis(xcex76-boratabenzene-3-yl)dimethylsilane]zirconium (II) 1,3-pentadiene,
[(xcex76-boratabenzene-3-yl) (xcex76-boratabenzene-4-yl)dimethylsilane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[(xcex76-boratabenzene-3-yl) (xcex76-boratabenzene-4-yl)dimethylsilane]zirconium (IV) dimethyl,
[(xcex76-boratabenzene-2-yl) (xcex76-boratabenzene-4-yl)dimethylsilane]zirconium (IV) dibenzyl,
[(xcex76-boratabenzene-2-yl) (xcex76-boratabenzene-4-yl)dimethylsilane]zirconium (IV) dichloride,
[bis(xcex76-boratabenzene-3-yl)dimethylsilane]zirconium (IV) dimethyl,
[(xcex76-boratabenzene-2-yl) (xcex76-boratabenzene-4-yl)dimethylsilane]zirconium (IV) dibenzyl,
[1-(xcex76-boratabenzene-2-yl)-2-(xcex76-boratabenzene-4-yl)ethane]hafnium (IV) dichloride
[1,2-bis(xcex76-boratabenzene-4-yl)ethane]zirconium (IV) dimethyl,
[1,2-bis(xcex76-boratabenzene-4-yl)ethane]zirconium (IV) dibenzyl,
[1,2-bis(xcex76-boratabenzene-4-yl)ethane]zirconium (IV) dichloride,
[1,2-bis(xcex76-boratabenzene-4-yl)ethane]zirconium (IV) dimethyl,
[1,2-bis(xcex76-boratabenzene-4-yl)ethane]zirconium (IV) dibenzyl,
[1,2-bis(xcex76-boratabenzene-4-yl)ethane]zirconium (IV) dichloride,
[1,2-bis(xcex76-boratabenzene-1-yl)ethane]zirconium (IV) dimethyl,
[1,2-bis(xcex76-boratabenzene-1-yl)ethane]zirconium (IV) dibenzyl,
[1,2-bis(xcex76-boratabenzene-1-yl)ethane]zirconium (IV) dichloride,
[1,2-bis(xcex76-boratabenzene-1-yl)ethane]zirconium (IV) dimethyl,
[1,2-bis(xcex76-boratabenzene-1-yl)ethane]zirconium (IV) dibenzyl,
[1,2-bis(xcex76-boratabenzene-1-yl)ethane]zirconium (IV) dichloride,
[2,2-bis(xcex76-boratabenzene-4-yl)propane]zirconium (IV) dimethyl,
[2,2-bis(xcex76-boratabenzene-4-yl)propane]zirconium (IV) dibenzyl,
[2,2-bis(xcex76-boratabenzene-4-yl)propane]zirconium (IV) dichloride,
[2,2-bis(xcex76-boratabenzene-4-yl)propane]zirconium (IV) dimethyl,
[2,2-bis(xcex76-boratabenzene-4-yl)propane]zirconium (IV) dibenzyl,
[2,2-bis(xcex76-boratabenzene-4-yl)propane]zirconium (IV) dichloride,
[2,2-bis(xcex76-boratabenzene-1-yl)propane]zirconium (IV) dimethyl,
[2,2-bis(xcex76-boratabenzene-1-yl)propane]zirconium (IV) dibenzyl,
[2,2-bis(xcex76-boratabenzene-1-yl)propane]zirconium (IV) dichloride,
[2,2-bis(xcex76-boratabenzene-1-yl)propane]zirconium (IV) dimethyl,
[2,2-bis(xcex76-boratabenzene-1-yl)propane]zirconium (IV) dibenzyl,
[2,2-bis(xcex76-boratabenzene-1-yl)propane]zirconium (IV) dichloride,
[1,2-bis(xcex76-boratabenzene-1-yl)ethane]hafnium (IV) dichloride, and
[2,2-bis(xcex76-boratabenzene-1-yl)propane]hafnium (IV) dichloride.
Further examples of preferred complexes according to the present invention correspond to the formula: 
wherein:
M is titanium, zirconium or hafnium, preferably titanium, in the +2, +3 or +4 formal oxidation state;
Z is a covalently bound, divalent substituent of up to 50 non-hydrogen atoms having the formula, xe2x80x94(ER22)mxe2x80x94, wherein E independently each occurrence is carbon, silicon or germanium, R2 independently each occurrence is selected from the group consisting of hydrocarbyl, hydrocarbyloxy, silyl, and germyl of up to 20 atoms other than hydrogen, and m is an integer from 1 to 3;
Y is a divalent derivative of a boratabenzene group or a hydrocarbyl-, dihydrocarbylamino-, silyl- or germyl-substituted boratabenzene group containing up to 50 nonhydrogen atoms that is bonded via its delocalized xcfx80-electrons to M;
R1 is a C1-20 hydrocarbyl group,
Xxe2x80x2 is a conjugated diene having from 4 to 30 non-hydrogen atoms, which forms a xcfx80-complex with M when M is in the +2 formal oxidation state, whereupon n is 1 and p is 0; and
Xxe2x80x3 each occurrence is an anionic ligand group that is covalently bonded to M when M is in the +3 or +4 formal oxidation state, whereupon n is 0 and p is 1 or 2, and optionally two Xxe2x80x3 groups together form a divalent anionic ligand group.
Examples of suitable Xxe2x80x2 moieties include: xcex76-1,4-diphenyl-1,3-butadiene; xcex74-1,3-pentadiene; xcex74-1-phenyl-1,3-pentadiene; xcex74-1,4-dibenzyl-1,3-butadiene; xcex74-2,4-hexadiene; xcex74-3-methyl-1,3-pentadiene; xcex74-1,4-ditolyl-1,3-butadiene; and xcex74-1,4-bis(trimethylsilyl)-1,3-butadiene. Of the foregoing 1,4-diphenyl-1,3-butadiene, 1-phenyl-1,3-pentadiene, and 2,4 hexadiene are preferred.
Examples of suitable Xxe2x80x3 moieties include chloride, methyl, benzyl, phenyl, tolyl, t-butyl, methoxide, and trimethylsilyl or two Xxe2x80x3 groups together are 1,4-butanediyl, s-cis(1,3-butadiene), or s-cis(2,3-dimethyl-1,3-butadiene).
Preferred Z groups are those wherein E is carbon and m is 2 or E is silicon and m is 1. In addition R2 is methyl, phenyl, methoxide, ethoxide, propoxide or butoxide.
In the most preferred embodiment xe2x80x94Zxe2x80x94Yxe2x80x94 is dimethyl(xcex76-1-phenylboratabenzene-4-yl)silyl, dimethyl(xcex76-1-N,N-dimethylaminoboratabenzene-4-yl)silyl, 1-(xcex76-1-phenylboratabenzene-4-yl)ethane-2-yl, or 1-(xcex76-1-N,N-dimethylamino)boratabenzene-4-yl)ethane-2-yl.
Examples of the foregoing metal complexes include:
[(t-butylamido)dimethyl(1-phenylboratabenzene-2-yl)silane]titanium dimethyl;
[(t-butylamido)dimethyl(1-phenylboratabenzene-3-yl)silane]titanium dimethyl;
[(t-butylamido)dimethyl(1-phenylboratabenzene-4-yl)silane]titanium dimethyl;
[(t-butylamido)dimethyl(1-N,N-dimethylaminoboratabenzene-2-yl)silane]titanium dimethyl;
[(t-butylamido)dimethyl(1-N,N-dimethylaminoboratabenzene-2-yl)silane]titanium dichloride;
[(t-butylamido)dimethyl(1-N,N-dimethylaminoboratabenzene-4-yl)silane]titanium(II) 1,4-diphenyl-1,3-butadiene;
[1-(t-butylamido)-2-(1-phenylboratabenzene-2-yl)ethane]titanium dimethyl,
[(t-butylamido)dimethyl(boratabenzene-2-yl)silane]titanium dimethyl;
[(t-butylamido)dimethyl(boratabenzene-3-yl)silane]titanium dimethyl;
[(t-butylamido)dimethyl(boratabenzene-4-yl)silane]titanium dimethyl;
[(t-butylamido)dimethyl(boratabenzene-4-yl)silane]titanium dibenzyl;
[(t-butylamido)dimethyl(boratabenzene-2-yl)silane]titanium dichloride;
[(t-butylamido)dimethyl(boratabenzene-4-yl)silane]titanium(II) 1,4-diphenyl-1,3-butadiene;
[1-(t-butylamido)-2-(boratabenzene-2-yl)ethane]titanium dimethyl
[(cyclohexylamido)dimethyl(1-phenyl)oratabenzene-2-yl)silane]titanium dimethyl;
[(cyclohexylamido)dimethyl(1-pheny)boratabenzene-3-yl)silane]titanium dimethyl;
[(cyclohexylamido)dimethyl(1-phenylboratabenzene-4-yl)silane]titanium dimethyl;
[(cyclohexylamido)dimethyl(1-N,N-dimethylaminoboratabenzene-2-yl)silane]titanium dimethyl;
[(cyclohexylamido)dimethyl(1-N,N-dimethylaminoboratabenzene-2-yl)silane]titanium dichloride;
[(cyclohexylamido)dimethyl(1-N,N-dimethylaminoboratabenzene-4-yl)silane]titanium(II) 1,4-diphenyl-1,3-butadiene;
[1-(cyclohexylamido)-2-(1-phenylboratabenzene-2-yl)ethane]titanium dimethyl,
(cyclohexylamido)dimethyl(boratabenzene-2-yl)silanetitanium dimethyl;
(cyclohexylamido)dimethyl(boratabenzene-3-yl)silanetitanium dimethyl;
(cyclohexylamido)dimethyl(boratabenzene-4-yl)silanetitanium dimethyl;
(cyclohexylamido)dimethyl(boratabenzene-4-yl)silanetitanium dibenzyl;
(cyclohexylamido)dimethyl(boratabenzene-2-yl)silanetitanium dichloride;
(cyclohexylamido)dimethyl(boratabenzene-4-yl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene; and
1-(cyclohexylamido)-2-(boratabenzene-2-yl)ethanetitanium dimethyl.
Still further examples of complexes according to the present invention correspond 
to the formula:
wherein:
M is titanium, zirconium or hafnium, preferably zirconium, in the +2, or +4 formal oxidation state;
Z is a covalently bound, divalent substituent of up to 50 non-hydrogen atoms having the formula, xe2x80x94(ER22)mxe2x80x94, wherein E independently each occurrence is carbon, silicon or germanium, R2 independently each occurrence is selected from the group consisting of hydrocarbyl, hydrocarbyloxy, silyl, and germyl of up to 20 atoms other than hydrogen, and m is an integer from 1 to 3;
Y is a divalent derivative of a boratabenzene group or a hydrocarbyl-, dihydrocarbylamino-, silyl- or germyl-substituted boratabenzene group containing up to 50 nonhydrogen atoms that is bonded via its delocalized xcfx80-electrons to M;
Xxe2x80x2 is a conjugated diene having from 4 to 30 non-hydrogen atoms, which forms a xcfx80-complex with M when M is in the +2 formal oxidation state, whereupon n is 1 and p is 0;
Xxe2x80x3 each occurrence is an anionic ligand group that is covalently bonded to M when M is in the +4 formal oxidation state, whereupon n is 0 and p is 2, and optionally two Xxe2x80x3 groups together form a divalent anionic ligand group; and
Rxe2x80x3xe2x80x3 is hydrogen, hydrocarbyl, silyl, halo-, cyano, dialkylamino, halohydrocarbyl, halocarbyl, dialkylamino substituted-hydrocarbyl, or hydrocarbyl-substituted metalloid wherein the metalloid is selected from Group 14 of the Periodic Table of the Elements, said Rxe2x80x3xe2x80x3, when a multi-atomic ligand group, containing up to 20 nonhydrogen atoms.
Preferably, Rxe2x80x3xe2x80x3 independently in each occurrence is selected from the group consisting of hydrogen, methyl, ethyl, and all isomers of propyl, butyl, pentyl and hexyl, as well as cyclopentyl, cyclohexyl, norbornyl, benzyl, and trimethylsilyl; or adjacent Rxe2x80x3xe2x80x3 groups are linked together thereby forming a fused ring system such as an indene-1-yl, 2-methylindene-1-yl, 3-methylindene-1-yl, 2,3-dimethylindene-1-yl, 2,3,5,6-tetramethylindene-1-yl, 2,3,5,6,7,pentamethylindene-1-yl, 2-methyl-4-phenylindene-1-yl, 2-methyl-4-naphthylindene-1-yl, tetrahydroindene-1-yl, fluorene-1-yl, tetrahydrofluorene-1-yl, or octahydrofluorene-1-yl group.
Most preferred complexes according to formula ilil are those containing a divalent derivative of a cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl, or octahydrofluorenyl group, or one of the foregoing groups further substituted with one or more methyl, ethyl, propyl, butyl, pentyl, hexyl, (including branched and cyclic isomers), norbornyl, benzyl, or phenyl groups.
Examples of suitable Xxe2x80x2 moieties include: xcex74-1,4-diphenyl-1,3-butadiene; xcex74-1,3-pentadiene; xcex74-1-phenyl-1,3-pentadiene; xcex74-1,4-dibenzyl-1,3-butadiene; xcex74-2,4-hexadiene; xcex74-3-methyl-1,3-pentadiene; xcex74-1,4-ditolyl-1,3-butadiene; and xcex74-1,4-bis(trimethylsilyl)-1,3-butadiene. Of the foregoing 1,4-diphenyl-1,3-butadiene, 1-phenyl-1,3-pentadiene, and 2,4 hexadiene are preferred.
Examples of suitable Xxe2x80x3 moieties include chloride, methyl, benzyl, phenyl, tolyl, t-butyl, methoxide, and trimethylsilyl or two Xxe2x80x3 groups together are 1,4-butanediyl, s-cis(1,3-butadiene), or s-cis(2,3-dimethyl-1,3-butadiene).
Preferred Z groups are those wherein E carbon and m is 2 or E is silicon and m is 1. Also preferably R2 is methyl, phenyl, methoxide, ethoxide, propoxide or butoxide.
In the most preferred embodiment xe2x80x94Zxe2x80x94Yxe2x80x94 is (xcex76-1-phenylboratabenzene-4-yl)dimethylsilyl, (xcex76-1-N,N-dimethylaminoboratabenzene-4-yl)dimethylsilyl, 1-(xcex76-1-phenylboratabenzene-4-yl)ethane-2-yl, 1-(xcex76-1-N,N-dimethylaminoboratabenzene-4-yl)ethane-2-yl, (xcex76-1-phenylboratabenzene-4-yl)phenylmethylsilyl, or (xcex76-(1-N,N-dimethylamino)boratabenzene-4-yl)phenylmethylsilyl.
Illustrative derivatives of Group 3, 4 or Lanthanide metals of the foregoing formula that may be employed in the practice of the present invention include:
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-tetramethylcyclopentadienyl)-silane]zirconium (II) 1,4-diphenyl-1,3-butadiene,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-tetramethylcyclopentadienyl)-silane]titanium (II) 1,3-pentadiene,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-tetramethylcyclopentadienyl)-silane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-tetramethylcyclopentadienyl)-silane]zirconium (IV) dimethyl,
[1-(xcex76-1-phenylboratabenzene-4-y1 )-2-(xcex75-tetramethylcyclopentadienyl)ethane]-zirconium (IV) dimethyl,
[1-(xcex76-1-methylboratabenzene-4-yl)-2-(xcex75-tetramethylcyclopentadienyl)ethane]-zirconium (IV) dimethyl,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-tetramethylcyclopentadienyl)-silane]zirconium (IV) dibenzyl,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-tetramethylcyclopentadienyl)-silane]zirconium (IV) dichloride,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-2-methylindenyl)silane]zirconium (II) 1,4-diphenyl-1,3-butadiene,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-2-methylindenyl)silane]zirconium (II) 1,3-pentadiene,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-2-methylindenyl)silane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-2-methylindenyl)silane]hafnium (IV) dimethyl,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-2-methylindenyl)silane]zirconium (IV) dibenzyl,
[(xcex76-1-methyl-2-phenylboratabenzene-4-yl)dimethyl(xcex75-2-methylindenyl)silane]-zirconium (IV) dibenzyl,
[1-(xcex76-1-methyl-2-phenylboratabenzene-4-yl)-2-(xcex75-2-methylindenyl)ethane]zirconium (IV) dibenzyl,
[1-(xcex76-1-methyl-2-phenylboratabenzene-4-yl)-2-(xcex75-2-methylindenyl)ethane]zirconium (IV) dimethyl,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-2-methylindenyl)silane]zirconium (IV) dichloride,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-3-methylindenyl)silane]zirconium (II) 1,4-diphenyl-1,3-butadiene,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-3-methylindenyl)silane]titanium (II) 1,3-pentadiene,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-3-methylindenyl)silane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-3-methylindenyl)silane]zirconium (IV) dimethyl,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-3-methylindenyl)silane]hafnium (IV) dibenzyl,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-3-methylindenyl)silane]zirconium (IV) dichloride,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-2,3-dimethylindenyl)silane]zirconiumn (II) 1,4-diphenyl-1,3-butadiene,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-2,3-dimethylindenyl)silane]titanium (II) 1,3-pentadiene,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-2,3-dimethylindenyl)silane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-2,3-dimethylindenyl)silane]zirconium (IV) dimethyl,
[(xcex76-1-](phenyl]boratabenzene-4-yl)dimethyl(xcex75-2,3-dimethylindenyl)silane]zirconium (IV) dibenzyl,
[1-(xcex76-1-methyl-2-(phenyl)boratabenzene-4-yl)-2-(xcex75-2,4-dimethylindenyl)ethane]zirconium (IV) dibenzyl,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-2,3-dimethylindenyl)silane]hafnium (IV) dichloride,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-2-methyl-4-phenylindenyl)-silane]zirconuim (II) 1,4-diphenyl-1,3-butadiene,
[(xcex76-1-methyl-2-phenylboratabenzene-4-yl)dimethyl(xcex75-2-methyl-4-phenylindenyl)-silane]zirconium (II) 1,4-diphenyl-1,3-butadiene,
[1-(xcex76-1-methyl-2-phenylboratabenzene-4-yl)-2-(xcex75-2-methyl-4-phenylindenyl)-ethane]zirconium (IV)dimethyl
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-2-methyl-4-phenylindenyl)silane]zirconium (II) 1,3-pentadiene,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-2-methyl-4-phenylindenyl)silane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-2-methyl-4-phenylindenyl)silane]zirconium (IV) dimethyl,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-2-methyl-4-phenylindenyl)silane]zirconium (IV) dibenzyl,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-2-methyl-4-phenylindenyl)silane]zirconium (IV) dichloride,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-tetrahydrofluorenyl)silane]titanium (II) 1,4-diphenyl-1,3-butadiene,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-tetrahydrofluorenyl)silane]zirconium (II) 1,3-pentadiene,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-tetrahydrofluorenyl)silane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[(xcex76-phenylboratabenzene-4-yl)dimethyl(xcex75-tetrahydrofluorenyl)silane]zirconium (IV) dimethyl,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-tetrahydrofluorenyl)silane]zirconium (IV) dibenzyl,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-tetrahydrofluorenyl)silane]hafnium (IV) dichloride,
[(xcex76-1-boratabenzene-4-yl)dimethyl (xcex75-tetramethylcyclopentadienyl)silane]zircronium (II) 1,4-diphenyl-1,3-butadiene,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-tetramethylcyclopentadienyl)silane]titanium (II) 1,3-pentadiene,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-tetramethylcyclopentadienyl)silane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-tetramethylcyclopentadienyl)silane]zirconium (IV) dimethyl,
[1-(xcex76-boratabenzene-4-yl)-2-(xcex75-tetramethylcyclopentadienyl)ethane]zirconium (IV) dimethyl,
[1-(xcex76-1-(methyl)boratabenzene-4-yl)-2-(xcex75-tetramethylcyclopentadienyl)-ethane]zirconium (IV) dimethyl,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-tetramethylcyclopentadienyl)silane]zirconium (IV) dibenzyl,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-tetramethylcyclopentadienyl)silane]zirconium (IV) dichloride,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-2-methylindenyl)silane]zirconium (II) 1,4-diphenyl-1,3-butadiene,
[(xcex76-1(phenyl)boratabenzene-4-yl)dimethyl(xcex75-2-methylindenyl)silane]zirconium (II) 1,3-pentadiene,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-2-methylindenyl)silane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-2-methylindenyl)silane]hafnium (IV) dimethyl,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-2-methylindenyl)silane]zirconium (IV) dibenzyl,
[(xcex76-1-methyl-2-(phenyl)boratabenzene-4-yl)dimethyl(xcex75-2-methylindenyl)silane]-zirconium (IV) dibenzyl,
[1-(xcex76-1-methyl-2-phenylboratabenzene-4-yl)-2-(xcex75-2-methylindenyl)ethane]zirconium (IV) dibenzyl,
[1-(xcex76-1-methyl-2-phenylboratabenzene-4-yl)-2-(xcex75-2-methylindenyl)ethane]zirconium (IV) dimethyl,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-2-methylindenyl)silane]zirconium (IV) dichloride,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-3-methylindenyl)silane]zirconium (II) 1,4-diphenyl-1,3-butadiene,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-3-methylindenyl)silane]titanium (II) 1,3-pentadiene,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-3-methylindenyl)silane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-3-methylindenyl)silane]zirconium (IV) dimethyl,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-3-methylindenyl)silane]hafnium (IV) dibenzyl,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-3-methylindenyl)silane]zirconium (IV) dichloride,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-2,3-dimethylindenyl)silane]zirconium (II) 1,4-diphenyl-1,3-butadiene,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-2,3-dimethylindenyl)silane]titanium (II) 1,3-pentadiene,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-2,3-dimethylindenyl)silane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-2,3-dimethylindenyl)silane]zirconium (IV) dimethyl,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-2,3-dimethylindenyl)silane]zirconium (IV) dibenzyl,
[1-(xcex76-1-methyl-2-(phenyl)boratabenzene-4-yl)-2-(xcex75-2,4-dimethylindenyl)ethane]zirconium (IV) dibenzyl,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-2,3-dimethylindenyl)silane]hafnium (IV) dichloride,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-2-methyl-4-phenylindenyl)silane]zirconiun (II) 1,4-diphenyl-1,3-butadiene,
[(xcex76-1-methyl-2-phenylboratabenzene-4-yl)dimethyl(xcex75-2-methyl-4-phenylindenyl)-silane]zirconium (II) 1,4-diphenyl-1,3-butadiene,
[1-(xcex76-1-methyl-2-(phenyl)boratabenzene-4-yl)-2-(xcex75-2-methyl-4-phenylindenyl)ethane]zirconium (IV)dimethyl
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-2-methyl-4-phenylindenyl)silane]zirconium (II) 1,3-pentadiene,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-2-methyl-4-phenylindenyl)silane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-2-methyl-4-phenylindenyl)silane]zirconium (IV) dimethyl,
[(xcex76-boratabenzene-4-yl)dimethyl((xcex75-2-methyl-4-phenylindenyl)silane]zirconium (IV) dibenzyl,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-2-methyl-4-phenylindenyl)silane]zirconium (IV) dichloride,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-tetrahydrofluorenyl)silane]titanium (II) 1,4-diphenyl-1,3-butadiene,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-tetrahydrofluorenyl)silane]zirconium (II) 1,3-pentadiene,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-tetrahydrofluorenyl)silane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-tetrahydrofluorenyl)silane]zirconium (IV) dimethyl,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-tetrahydrofluorenyl)silane]zirconium (IV) dibenzyl,
[(xcex76-boratabenzene-4-yl)dimethyl(xcex75-tetrahydrofluorenyl)silane]hafnium (IV) dichloride,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-tetramethylcyclopentadienyl)-silane]zirconium (II) 1,4-diphenyl-1,3-butadiene,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-tetramethylcyclopentadienyl)-silane]titanium (II) 1,3-pentadiene,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-tetramethylcyclopentadienyl)-silane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[(xcex76-phenylboratabenzene-4-yl)dimethyl(xcex75-tetramethylcyclopentadienyl)-silane]zirconium (IV) dimethyl,
[1-(xcex76-1-phenylboratabenzene-4-yl)-2-(xcex75-tetramethylcyclopentadienyl)ethane]zirconium (IV) dimethyl,
[1-(xcex76-1-(methyl)boratabenzene-4-yl)-2-(xcex75-tetramethylcyclopentadienyl)ethane]zirconium (IV) dimethyl,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-tetramethylcyclopentadienyl)-silane]zirconium (IV) dibenzyl,
[(xcex76-1-phenylboratabenzene-4-yl)dimethyl(xcex75-tetramethylcyclopentadienyl)-silane]zirconium (IV) dichloride,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-2-methylindenyl)silane]zirconium (II) 1,4-diphenyl-1,3-butadiene,
[xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl((xcex75-2-methylindenyl)silane]zirconium (II) 1,3-pentadiene,
[xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-2-methylindenyl)silane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-2-methylindenyl)silane]hafnium (IV) dimethyl,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-2-methylindenyl)silane]zirconium (IV) dibenzyl,
[(xcex76-1-diisopropylamino-3-phenylboratabenzene-4-yl)dimethyl(xcex75-2-methylindenyl)silane]zirconium (IV) dibenzyl,
[1-(xcex76-1-diisopropylamino-2-phenylboratabenzene-4-yl)-2-(xcex75-2-methylindenyl)ethane]zirconium (IV) dibenzyl,
[1-(xcex76-1-diisopropylamino-2-phenylboratabenzene-4-yl)-2-(xcex75-2-methylindenyl)ethane]zirconium (IV) dimethyl,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-2-methylindenyl)silane]zirconium (IV) dichloride,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-3-methylindenyl)silane]zirconium (II) 1,4-diphenyl-1,3-butadiene,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-3-methylindenyl)silane]titanium (II) 1,3-pentadiene,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-3-methylindenyl)silane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-3-methylindenyl)silane]zirconium (IV) dimethyl,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-3-methylindenyl)silane]hafnium (IV) dibenzyl,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-3-methylindenyl)silane]zirconium (IV) dichloride,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-2,3-dimethylindenyl)silane]zirconium (II) 1,4-diphenyl-1,3-butadiene,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-2,3-dimethylindenyl)silane]titanium (II) 1,3-pentadiene,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-2,3-dimethylindenyl)-silane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-2,3-dimethylindenyl)silane]zirconium (IV) dimethyl,
[(xcex76-1-(N,N-diisopropylamino)boratabenzene-4-yl)dimethyl(xcex75-2,3-dimethylindenyl)silane]zirconium (IV) dibenzyl,
[1-(xcex76-1-diisopropylamino-2-(phenyl)boratabenzene-4-yl)-2-(xcex75-2,4-dimethylindenyl)ethane]zirconium (IV) dibenzyl,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-2,3-dimethylindenyl)silane]hafnium (IV) dichloride,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-2-methyl-4-phenylindenyl)silane]zirconium (II) 1,4-diphenyl-1,3-butadiene,
[(xcex76-1-diisopropylamino-2-phenylboratabenzene-4-yl)dimethyl(xcex75-2-methyl-4-phenylindenyl)silane]zirconium (II) 1,4-diphenyl-1,3-butadiene,
[1-(xcex76-1-diisopropylamino-2-phenylboratabenzene-4-yl)-2-(xcex75-2-methyl-4-phenylindenyl)ethane]zirconium (IV)dimethyl
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-2-methyl-4-phenylindenyl)silane]zirconium (II) 1,3-pentadiene,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-2-methyl-4-phenylindenyl)silane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-2-methyl-4-phenylindenyl)silane]zirconium (IV) dimethyl,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-2-methyl-4-phenylindenyl)silane]zirconium (IV) dibenzyl,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-2-methyl-4-phenylindenyl)silane]zirconium (IV) dichloride,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-tetrahydrofluorenyl)-silane]titanium (II) 1,4-diphenyl-1,3-butadiene,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-tetrahydrofluorenyl)-silane]zirconium (II) 1,3-pentadiene,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-tetrahydrofluorenyl)-silane]titanium (III) 2-(N,N-dimethylamino)benzyl,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-tetrahydrofluorenyl)-silane]zirconium (IV) dimethyl,
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-tetrahydrofluorenyl)-silane]zirconium (IV) dibenzyl, and
[(xcex76-1-N,N-diisopropylaminoboratabenzene-4-yl)dimethyl(xcex75-tetrahydrofluorenyl)-silane]hafnium (IV) dichloride.
Other metal complexes, especially compounds containing other Group 3, 4 or Lanthanide metals will, of course, be apparent to those skilled in the art. In addition other substituted boratabenzene ligands especially 1-benzyl, and 1-methyl substituted boratabenzenes will similarly be apparent to those skilled in the art.
The complexes are rendered catalytically active by combination with an activating cocatalyst or by use of an activating technique. Suitable activating cocatalysts for use herein include polymeric or oligomeric alumoxanes, especially methylalumoxane, triisobutyl aluminum-modified methylalumoxane, or diisobutylalumoxane; strong Lewis acids, such as C1-30 hydrocarbyl substituted Group 13 compounds, especially tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron- compounds and halogenated derivatives thereof, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, especially tris(pentafluorophenyl)borane; and nonpolymeric, inert, compatible, noncoordinating, ion forming compounds (including the use of such compounds under oxidizing conditions). A suitable activating technique is bulk electrolysis (explained in more detail hereinafter). Combinations of the foregoing activating cocatalysts and techniques may also be employed if desired. The foregoing activating cocatalysts and activating techniques have been previously taught with respect to different metal complexes in the following references: EP-A-277,003, U.S. Pat. No. 5,153,157, U.S. Pat. No. 5,064,802, EP-A-468,651, EP-A-520,732 and WO93/23412.
Suitable nonpolymeric, inert, compatible, noncoordinating, ion forming compounds useful as cocatalysts in one embodiment of the present invention comprise a cation which is a Bronsted acid capable of donating a proton, and a compatible, noncoordinating, anion, Axe2x88x92. Preferred anions are those containing a single coordination complex comprising a charge-bearing metal or metalloid core which anion is capable of balancing the charge of the active catalyst species (the metal cation) which is formed when the two components are combined. Also, said anion can be displaced by olefinic, diolefinic and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers or nitrites. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon. Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom are well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially.
Additional suitable anions include sterically shielded diboron anions corresponding to the formula: 
wherein:
S is alkyl, fluoroalkyl, aryl, or fluoroaryl (and where two S groups are present additionally hydrogen),
ArF is fluoroaryl, and
X1 is either hydrogen or halide.
Such diboron anions are disclosed in U.S. Pat. No. 5,447,895.
Preferably such cocatalysts may be represented by the following general formula:
(L*xe2x88x92H)+dAdxe2x88x92
wherein:
L* is a neutral ligand;
(L*xe2x88x92H)+ is a Bronsted acid;
Adxe2x88x92 is a noncoordinating, compatible anion having a charge of d-, and
d is an integer from 1 to 3.
More preferably d is one, that is, Adxe2x88x92 is Axe2x88x92.
Highly preferably, Axe2x88x92 corresponds to the formula: [BQ4]xe2x88x92
wherein:
B is boron in the +3 formal oxidation state; and
Q independently each occurrence is selected from hydride, dialkylamino, halide, alkoxide, aryloxide, hydrocarbyl, halocarbyl, and halosubstituted-hydrocarbyl radicals, said Q having up to 20 carbons with the proviso that in not more than one occurrence is Q halide.
In a more highly preferred embodiment, Q is a fluorinated C1-20 hydrocarbyl group, most preferably, a fluorinated aryl group, especially, pentafluorophenyl.
Illustrative, but not limiting, examples of ion forming compounds comprising proton donatable cations which may be used as activating cocatalysts in the preparation of the catalysts of this invention are tri-substituted ammonium salts such as:
trimethylammonium tetraphenylborate,
triethylammonium tetraphenylborate,
tripropylammonium tetraphenylborate,
tri(n-butyl)ammonium tetraphenylborate,
tri(t-butyl)ammonium tetraphenylborate,
N,N-dimethylanilinium tetraphenylborate,
N,N-diethylanilinium tetraphenylborate,
N,N-dimethyl(2,4,6-trimethylanilinium) tetraphenylborate, trimethylammonium tetrakis-(penta-fluorophenyl) borate, triethylammonium tetrakis-(pentafluorophenyl) borate,
tripropylammonium tetrakis(pentafluorophenyl) borate, tri(n-butyl)-ammonium tetrakis(pentafluorophenyl) borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)
borate, N,N-diethylanilinium tetrakis(pentafluoro-phenyl) borate, N,N-dimethyl(2,4,6-trimethyl-anilinium) tetrakis-(pentafluorophenyl) borate,
trimethylammonium tetrakis(2,3,4,6-tetrafluorophenylborate,
triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate,
tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate,
tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate,
dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate,
N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl) borate,
N,N-diethylanilinium tetrakis(2,3,4,6-letrafluorophenyl) borate, and N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis-(2,3,4,6-tetrafluorophenyl) borate.
Dialkyl ammonium salts such as:
di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate, and
dicyclohexylammonium tetrakis(pentafluorophenyl) borate.
Tri-substituted phosphonium salts such as: triphenylphosphonium tetrakis(pentafluorophenyl) borate, tri(o-tolyl)phosphonium tetrakis(penta-fluorophenyl) borate, and
tri(2,6-dimethylphenyl)-phosphonium tetrakis(penta-fluorophenyl) borate.
Preferred are N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and tributylammonium tetrakis(pentafluorophenyl)borate.
Another suitable ion forming, activating cocatalyst comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula:
(Oxe+)d(Adxe2x88x92)e
wherein:
Oxe+ is a cationic oxidizing agent having charge e+;
e is an integer from 1 to 3; and
Adxe2x88x92, and d are as previously defined.
Examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag+, or Pb+2. Preferred embodiments of Adxe2x88x92 are those anions previously defined with respect to the Bronsted acid containing activating cocatalysts, especially tetrakis(pentafluorophenyl)borate.
Another suitable ion forming, activating cocatalyst comprises a compound which is a salt of a carbenium ion or silylium ion and a noncoordinating, compatible anion represented by the formula:
ĉ+Axe2x88x92
wherein:
ĉ+ is a C1-20 carbenium ion or silylium ion; and
Axe2x88x92 is as previously defined.
A preferred carbenium ion is the trityl cation, that is triphenylcarbenium. A preferred silylium ion is triphenylsilylium.
The foregoing activating technique and ion forming cocatalysts are also preferably used in combination with a tri(hydrocarbyl)aluminum compound having from 1 to 4 carbons in each hydrocarbyl group, an oligomeric or polymeric alumoxane compound, or a mixture of a tri(hydrocarbyl)aluminum compound having from 1 to 4 carbons in each hydrocarbyl group and a polymeric or oligomeric alumoxane.
An especially preferred activating cocatalyst comprises the combination of a trialkyl aluminum compound having from 1 to 4 carbons in each alkyl group and an ammonium salt of tetrakis(pentafluorophenyl)borate, in a molar ratio from 0.1:1 to 1:0.1, optionally up to 1000 mole percent of an alkylalumoxane with respect to M, is also present.
The activating technique of bulk electrolysis involves the electrochemical oxidation of the metal complex under electrolysis conditions in the presence of a supporting electrolyte comprising a noncoordinating, inert anion. In the technique, solvents, supporting electrolytes and electrolytic potentials for the electrolysis are used such that electrolysis byproducts that would render the metal complex catalytically inactive are not substantially formed during the reaction. More particularly, suitable solvents are materials that are: liquids under the conditions of the electrolysis (generally temperatures from 0 to 100xc2x0 C.), capable of dissolving the supporting electrolyte, and inert. xe2x80x9cInert solventsxe2x80x9d are those that are not reduced or oxidized under the reaction conditions employed for the electrolysis. It is generally possible in view of the desired electrolysis reaction to choose a solvent and a supporting electrolyte that are unaffected by the electrical potential used for the desired electrolysis. Preferred solvents include difluorobenzene (all isomers), DME, and mixtures thereof.
The electrolysis may be conducted in a standard electrolytic cell containing an anode and cathode (also referred to as the working electrode and counter electrode respectively). Suitably materials of construction for the cell are glass, plastic, ceramic and glass coated metal. The electrodes are prepared from inert conductive materials, by which are meant conductive materials that are unaffected by the reaction mixture or reaction conditions. Platinum or palladium are preferred inert conductive materials. Normally, an ion permeable membrane such as a fine glass frit separates the cell into separate compartments, the working electrode compartment and counter electrode compartment. The working electrode is immersed in a reaction medium comprising the metal complex to be activated, solvent, supporting electrolyte, and any other materials desired for moderating the electrolysis or stabilizing the resulting complex. The counter electrode is immersed in a mixture of the solvent and supporting electrolyte. The desired voltage may be determined by theoretical calculations or experimentally by sweeping the cell using a reference electrode such as a silver electrode immersed in the cell electrolyte. The background cell current, the current draw in the absence of the desired electrolysis, is also determined. The electrolysis is completed when the current drops from the desired level to the background level. In this manner, complete conversion of the initial metal complex can be easily detected.
Suitable supporting electrolytes are salts comprising a cation and an inert, compatible, noncoordinating anion, Axe2x88x92. Preferred supporting electrolytes are salts corresponding to the formula:
G+Axe2x88x92;
wherein:
G+ is a cation which is nonreactive towards the starting and resulting complex, and
Axe2x88x92 is a noncoordinating, compatible anion.
Examples of cations, G+, include tetrahydrocarbyl substituted ammonium or phosphonium cations having up to 40 nonhydrogen atoms. A preferred cation is the tetra-n-butylammonium cation.
During activation of the complexes of the present invention by bulk electrolysis the cation of the supporting electrolyte passes to the counter electrode and Axe2x88x92 migrates to the working electrode to become the anion of the resulting oxidized product. Either the solvent or the cation of the supporting electrolyte is reduced at the counter electrode in equal molar quantity with the amount of oxidized metal complex formed at the working electrode.
Preferred supporting electrolytes are tetrahydrocarbylammonium salts of tetrakis(perfluoroaryl) borates having from 1 to 10 carbons in each hydrocarbyl group, especially tetra-n-butylammonium tetrakis(pentafluorophenyl) borate.
The molar ratio of catalysticocatalyst employed preferably ranges from 1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most preferably from 1:10 to 1:2.
In general, the catalysts can be prepared by combining the two components (metal complex and activator) in a suitable solvent at a temperature within the range from xe2x88x92100xc2x0 C. to 300xc2x0 C. The catalyst may be separately prepared prior to use by combining the respective components or prepared in situ by combination in the presence of the monomers to be polymerized. It is preferred to form the catalyst in situ due to the exceptionally high catalytic effectiveness of catalysts prepared in this manner. The catalysts"" components are sensitive to both moisture and oxygen and should be handled and transferred in an inert atmosphere.
As previously mentioned the present metal complexes are highly desirable for use in preparing supported catalysts. In this regard, the presence of the alkoxy functionality in the bridging group is particularly beneficial in allowing the complexes to chemically bind to hydroxyl, silane or chlorosilane functionality of the substrate materials. Especially suited substrates include alumina or silica. Suitable supported catalyst systems are readily prepared by contacting the present metal complexes with the substrate optionally while subjecting to heating and/or reduced pressures. A Lewis base, especially a trialkylamine can be present to assist in the reaction between the support and the alkoxy functionality of the metal complexes if desired.
Preferred supports for use in the present invention include highly porous silicas, aluminas, aluminosilicates, and mixtures thereof. The most preferred support material is silica. The support material may be in granular, agglomerated, pelletized, or any other physical form. Suitable materials include, but are not limited to, silicas available from Grace Davison (division of W.R. Grace and Co.) under the designations SD 3216.30, Davison Syloid 245, Davison 948 and Davison 952, and from Degussa AG under the designation Aerosil 812; and aluminas available from Akzo Chemicals Inc. under the designation Ketzen Grade B.
Supports suitable for the present invention preferably have a surface area as determined by nitrogen porosimetry using the B.E.T. method from 10 to 1000 m2/g, and preferably from 100 to 600 m2/g. The pore volume of the support, as determined by nitrogen adsorption, advantageously is between 0.1 and 3 cm3/g, preferably from 0.2 to 2 cm3/g. The average particle size is not critical, but typically is from 0.5 to 500 xcexcm, preferably from 1 to 100 xcexcm.
Both silica and alumina are known to inherently possess small quantities of hydroxyl functionality attached to the crystal structure. When used as a support herein, these materials are preferably subjected to a heat treatment and/or chemical treatment to reduce the hydroxyl content thereof. Typical heat treatments are carried out at a temperature from 30 to 1000xc2x0 C. for a duration of 10 minutes to 50 hours in an inert atmosphere or under reduced pressure. Typical chemical treatments include contacting with Lewis acid alkylating agents such as trihydrocarbyl aluminum compounds, trihydrocarbylchlorosilane compounds, trihydrocarbylalkoxysilane compounds or similar agents. Preferred silica or alumina materials for use herein have a surface hydroxyl content that is less than 0.8 mmol hydroxyl groups per gram of solid support, more preferably less than 0.5 mmol per gram. The hydroxyl content may be determined by adding an excess of dialkyl magnesium to a slurry of the solid support and determining the amount of dialkyl magnesium remaining in solution via known techniques. This method is based on the reaction:
Sxe2x80x94OH+Mg(Alk)2xe2x86x92Sxe2x80x94OMg(Alk)+(Alk)H,
wherein S is the solid support, and Alk is a C1-4 alkyl group.
The support may be unfunctionalized (excepting for hydroxyl groups as previously disclosed) or functionalized by treating with a silane or chlorosilane functionalizing agent to attach thereto pendant silane xe2x80x94(Sixe2x80x94R)xe2x95x90, or chlorosilane xe2x80x94(Sixe2x80x94Cl)xe2x95x90 functionality, wherein R is a C1-10 hydrocarbyl group. Suitable functionalizing agents are compounds that react with surface hydroxyl groups of the support or react with the silicon or aluminum of the matrix. Examples of suitable functionalizing agents include phenylsilane, diphenylsilane, methylphenylsilane, dimethylsilane, diethylsilane, dichlorosilane, and dichlorodimethylsilane. Techniques for forming such functionalized silica or alumina compounds were previously disclosed in U.S. Pat. No. 3,687,920 and U.S. Pat. No. 3,879,368.
The support may also be treated with an aluminum component selected from an alumoxane or an aluminum compound of the formula AlR4xR5yxe2x80x2, wherein R4 independently each occurrence is hydride or C1-20 hydrocarbyl, R5 is hydride,C1-10 hydrocarbyl or C1-10 hydrocarbyloxy, xxe2x80x2 is 2 or 3, yxe2x80x2 is 0 or 1 and the sum of xxe2x80x2 and yxe2x80x2 is 3. Examples of suitable R4 and R5 groups include methyl, methoxy, ethyl, ethoxy, propyl (all isomers), propoxy (all isomers), butyl (all isomers), butoxy (all isomers), phenyl, phenoxy, benzyl, and benzyloxy. Preferably, the aluminum component is selected from the group consisting of aluminoxanes and tri(C1-4 hydrocarbyl)aluminum compounds. Most preferred aluminum components are aluminoxanes, trimethyl aluminum, triethyl aluminum, tri-isobutyl aluminum, and mixtures thereof.
Alumoxanes (also referred to as aluminoxanes) are oligomeric or polymeric aluminum oxy compounds containing chains of alternating aluminum and oxygen atoms, whereby the aluminum carries a substituent, preferably an alkyl group. The structure of alumoxane is believed to be represented by the following general formulae (xe2x80x94Al(R6)xe2x80x94O)mxe2x80x2, for a cyclic alumoxane, and R62Alxe2x80x94O(xe2x80x94Al(R6)xe2x80x94O)mxe2x80x2xe2x80x94AlR62, for a linear compound, wherein R6 is C1-10 alkyl, and mxe2x80x2 is an integer ranging from 1 to 50, preferably at least 4. Alumoxanes are typically the reaction products of water and an aluminum alkyl, which in addition to an alkyl group may contain halide or alkoxide groups. Reacting several different aluminum alkyl compounds, such as for example trimethyl aluminum and tri-isobutyl aluminum, with water yields so-called modified or mixed alumoxanes. Preferred alumoxanes are methylalumoxane and methylalumoxane modified with minor amounts of C2-4 alkyl groups, especially isobutyl. Alumoxanes generally contain minor to substantial amounts of starting aluminum alkyl compound.
Particular techniques for the preparation of alumoxane type compounds by contacting an aluminum alkyl compound with an inorganic salt containing water of crystallization are disclosed in U.S. Pat. No. 4,542,119. In a particular preferred embodiment an aluminum alkyl compound is contacted with a regeneratable water-containing substance such as hydrated alumina, silica or other substance. This is disclosed in EP-A-338,044. Thus the alumoxane may be incorporated into the support by reaction of a hydrated alumina or silica material, which has optionally been functionalized with silane, siloxane, hydrocarbyloxysilane, or chlorosilane groups, with a tri(C1-10 alkyl) aluminum compound according to known techniques.
The treatment of the support material in order to also include optional alumoxane or trialkylaluminum loadings involves contacting the same before, after or simultaneously with addition of the complex or activated catalyst hereunder with the alumoxane or trialkylaluminum compound, especially triethylaluminum or triisobutylaluminum. Optionally the mixture can also be heated under an inert atmosphere for a period and at a temperature sufficient to fix the alumoxane, trialkylaluminum compound, complex or catalyst system to the support. Optionally, the treated support component containing alumoxane or the trialkylaluminum compound may be subjected to one or more wash steps to remove alumoxane or trialkylaluminum not fixed to the support.
Besides contacting the support with alumoxane the alumoxane may be generated in situ by contacting an unhydrolyzed silica or alumina or a moistened silica or alumina with a trialkyl aluminum compound optionally in the presence of an inert diluent. Such a process is well known in the art, having been disclosed in EP-A-250,600, U.S. Pat. No. 4,912,075, and U.S. Pat. No. 5,008,228. Suitable aliphatic hydrocarbon diluents include pentane, isopentane, hexane, heptane, octane, isooctane, nonane, isononane, decane, cyclohexane, methylcyclohexane and combinations of two or more of such diluents. Suitable aromatic hydrocarbon diluents are benzene, toluene, xylene, and other alkyl or halogen substituted aromatic compounds. Most preferably, the diluent is an aromatic hydrocarbon, especially toluene. After preparation in the foregoing manner the residual hydroxyl content thereof is desirably reduced to a level less than 1.0 meq of OH per gram of support, by any of the previously disclosed techniques.
The catalysts, whether or not supported in any of the foregoing methods, may be used to polymerize ethylenically and/or acetylenically unsaturated monomers having from 2 to 100,000 carbon atoms either alone or in combination. Preferred monomers include the C2-20 xcex1-olefins especially ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, long chain macromolecular xcex1-olefins, and mixtures thereof. Other preferred monomers include styrene, C1-4 alkyl substituted styrene, tetrafluoroethylene, vinylbenzocyclobutane, ethylidenenorbornene, 1,4-hexadiene, 1,7-octadiene, vinylcyclohexane, 4-vinylcyclohexene, divinylbenzene, and mixtures thereof with ethylene. Long chain macromolecular xcex1-olefins are vinyl terminated polymeric remnants formed in situ during continuous solution polymerization reactions. Under suitable processing conditions such long chain macromolecular units are readily polymerized into the polymer product along with ethylene and other short chain olefin monomers to give small quantities of long chain branching in the resulting polymer.
The catalysts of the invention are particularly adapted for use in the preparation of high molecular weight xcex1-olefin homopolymers and copolymers, especially crystalline propylene homopolymers and copolymers having a high degree of isotacticity. In this regard the preferred catalysts are the corresponding racemic isomers of the metal complexes disclosed herein.
In general, the polymerization may be accomplished at conditions well known in the prior art for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, such as temperatures from 0-250xc2x0 C. and pressures from atmospheric to 1000 atmospheres (0.1 to 100 MPa). Suspension, solution, slurry, gas phase or other process conditions may be employed if desired. The support, if present, is preferably employed in an amount to provide a weight ratio of catalyst (based on metal):support from 1:100,000 to 1:10, more preferably from 1:50,000 to 1:20, and most preferably from 1:10,000 to 1:30. Suitable gas phase reactions may utilize condensation of the monomer or monomers employed in the reaction, or of an inert diluent to remove heat from the reactor.
In most polymerization reactions the molar ratio of catalyst:polymerizable compounds employed is from 10xe2x88x9212:1 to 10xe2x88x921:1, more preferably from 10xe2x88x9212:1 to 10xe2x88x925:1.
Suitable solvents for polymerization via a solution process are noncoordinating, inert liquids. Examples include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; perfluorinated hydrocarbons such as perfluorinated C4-10 alkanes, and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, and xylene. Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1-butene, butadiene, cyclopentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1,7-octadiene, 1-octene, 1-decene, styrene, divinylbenzene, ethylidenenorbornene, allylbenzene, vinyltoluene (including all isomers alone or in admixture), 4-vinylcyclohexene, and vinylcyclohexane. Mixtures of the foregoing are also suitable.
The catalysts may also be utilized in combination with at least one additional homogeneous or heterogeneous polymerization catalyst in the same or in separate reactors connected in series or in parallel to prepare polymer blends having desirable properties. An example of such a process is disclosed in WO 94/00500. Alternatively, the two catalysts may be utilized in sequential or simultaneous polymerizations while being supported on a highly porous support or carrier, including a prepolymerized support that is capable of being permeated by an xcex1-olefin.
Such polymerization process may comprise contacting, optionally in a solvent or in a nonsolvent, one or more xcex1-olefins with a catalyst according to the present invention, in one or more continuous stirred tank or tubular reactors, or in the absence of solvent, optionally in one or more fluidized bed gas phase reactors, connected in series or parallel, and recovering the resulting polymer. Condensed monomer or solvent may be added to the gas phase reactor as is well known in the art. In the preparation of polypropylene the foregoing polymerization may further involve use of a porous inert carrier particle which optionally may be prepolymerized with polypropylene or other polymer.
In another process an ethylene/xcex1-olefin interpolymer composition is prepared by:
(A) contacting ethylene and at least one other xcex1-olefin under polymerization conditions in the presence of a catalyst composition of the present invention in at least one reactor to produce a first interpolymer or optionally a solution of a first interpolymer,
(B) contacting ethylene and at least one other xcex1-olefin under polymerization conditions and at a higher polymerization reaction temperature than used in step (A) in the presence of a heterogeneous Ziegler catalyst in at least one other reactor to produce a second interpolymer optionally in solution, and
(C) combining the first interpolymer and second interpolymer to form an ethylene/xcex1-olefin interpolymer blend composition, and
(D) recovering the ethylene/xcex1-olefin interpolymer blend composition.
Preferably the heterogeneous Ziegler catalyst comprises:
(i) a solid support component comprising magnesium halide, silica, modified silica, alumina, aluminum phosphate, or a mixture thereof, and
(ii) a transition metal component represented by the formula:
TrXxe2x80x2xe2x80x3u(OR6)vxe2x88x92u, TrXxe2x80x2xe2x80x3uR6vxe2x88x92u, VOXxe2x80x2xe2x80x33 or VO(OR6)3,
wherein:
Tr is a Group 4, 5, or 6 metal,
u is a number from 0 to 6 that is less than or equal to v,
v is the formal oxidation number of Tr,
Xxe2x80x2xe2x80x3 is halogen, and
R6 independently each occurrence is a C1-10 alkyl group.
These polymerizations are generally carried out under solution conditions to facilitate the intimate mixing of the two polymer-containing streams. The foregoing technique allows for the preparation of ethylene/xcex1-olefin interpolymer compositions having a broad range of molecular weight distribution and composition distribution. Preferably, the heterogeneous catalyst is also chosen from those catalysts which are capable of efficiently producing the polymers under high temperature, especially, temperatures greater than or equal to 180xc2x0 C. under solution process conditions.
In a still further embodiment, there is provided a process for preparing polypropylene homopolymer or copolymer compositions, comprising:
(A) polymerizing propylene and, optionally, at least one other xcex1-olefin in a solution, slurry or gas phase process under suitable polymerization temperatures and pressures in at least one reactor containing a catalyst composition of the present invention, optionally supported on an inert support to produce a first polymer,
(B) optionally passing the polymer of (A) into at least one other reactor in the presence of one other xcex1-olefin under polymerization conditions to form a polypropylene/propylene/xcex1-olefin interpolymer composition blend, and
(C) recovering the resulting composition.
The foregoing technique also allows for the preparation of polypropylene and polypropylene/propylene/xcex1-olefin interpolymer composition blends having a broad range of molecular weight distributions and composition distributions. Particularly desirable xcex1-olefins for use in the foregoing processes are ethylene, C4-8 xcex1-olefins, most desirably ethylene.
The skilled artisan will appreciate that the invention disclosed herein may be practiced in the absence of any component which has not been specifically disclosed.